CN114478911B - Amphoteric acrylic polymer retanning agent and preparation method thereof - Google Patents
Amphoteric acrylic polymer retanning agent and preparation method thereof Download PDFInfo
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- CN114478911B CN114478911B CN202210090920.1A CN202210090920A CN114478911B CN 114478911 B CN114478911 B CN 114478911B CN 202210090920 A CN202210090920 A CN 202210090920A CN 114478911 B CN114478911 B CN 114478911B
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- acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
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Abstract
The invention discloses a preparation method of an amphoteric acrylic polymer retanning agent, which is characterized in that an acrylamide alkyl cationic monomer and acrylic acid/methacrylic acid are selected, and the amphoteric acrylic polymer retanning agent is obtained by free radical polymerization under a strong alkaline condition by adopting a mixed initiation system of ammonium persulfate and sodium hypophosphite. The amphoteric acrylic polymer retanning agent still keeps clear and transparent at isoelectric points, does not generate precipitates, can greatly improve the distribution uniformity of amphoteric acrylic polymers in leather, and obviously enhances the retanning application effect.
Description
Technical Field
The invention belongs to the technical field of leather, and particularly discloses an amphoteric acrylic polymer retanning agent and a preparation method thereof.
Background
The amphoteric acrylic polymer retanning agent can adjust the charge property of leather, particularly chrome-free tanned leather, realize the balance of permeation and combination of dyeing and finishing materials and improve the performance of the leather, so that the amphoteric acrylic polymer retanning agent is more and more concerned in the application of a chrome-free tanning system. The molecular chain of the amphoteric acrylic polymer retanning agent contains anionic and cationic groups, the charge of the amphoteric acrylic polymer retanning agent changes with the difference of bath solution pH, and the amphoteric acrylic polymer retanning agent has an isoelectric point. It is noted that when the pH is near the isoelectric point, strong electrostatic interaction occurs between the anionic groups and the anionic groups in/between chains of the conventional amphoteric acrylic polymer retanning agents, which easily causes serious aggregation and precipitation (strong, gentle, guobaoshu, etc.; synthesis and application of amphoteric acrylic resin retanning agents [ J ]. chinese leather, 2004, 33(15): 7-10.), is not favorable for uniform permeation and distribution in the leather, and seriously hinders the application effect thereof.
Cationic monomers of the existing amphoteric acrylic retanning agents are mainly diallyl ammonium chloride cationic monomers DMDAAC, DEDAAC and the like, or acryloyl oxyalkyl quaternary ammonium salt cationic monomers DMC, DAC and the like (such as CN109627376A, an amphoteric polymer auxiliary agent, a preparation method and application thereof). But the diallyl ammonium chloride cationic monomer has the defect of reduced reactivity in the polymerization reaction; the acrylic acyloxy alkyl quaternary ammonium salt cationic monomer contains ester functional groups, so that the polymer has the defect of easy hydrolysis. Meanwhile, the pH value of the polymerization in the prior art is usually under an acidic condition, and the initiator is mainly selected from persulfate or a redox system. This results in a severe precipitation of the amphoteric acrylic retanning agent product at the isoelectric point.
In view of this, the invention is particularly proposed.
Disclosure of Invention
To solve the problems of the background art, a first object of the present invention is to provide a method for preparing an amphoteric acrylic polymer retanning agent, by which the amphoteric acrylic polymer retanning agent prepared remains clear and transparent at the isoelectric point without precipitation.
The second purpose of the invention is to provide the amphoteric acrylic polymer retanning agent obtained by the preparation method.
In order to achieve the above purpose, the first technical scheme adopted by the invention is as follows:
the preparation method of the amphoteric acrylic polymer retanning agent comprises the following steps:
mixing the first component with an acrylamide alkyl cationic monomer, controlling the pH to be 9.0-13.5, carrying out polymerization reaction under the action of an initiator, and cooling;
wherein the first component is acrylic acid or methacrylic acid;
the initiator is a mixed system of ammonium persulfate and sodium hypophosphite.
Preferably, the acrylamide alkyl cationic monomer includes any one of dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, methacryl propyl trimethyl ammonium chloride and (3-acrylamidopropyl) trimethyl ammonium chloride.
Preferably, the first component is 35-45 parts by weight, and the acrylamide alkyl cationic monomer is 25-140 parts by weight.
Preferably, the mass of the ammonium persulfate is 1-5% of the total mass of the first component and the acrylamide alkyl cationic monomer, and the mass of the sodium hypophosphite is 0.1-7% of the total mass of the first component and the acrylamide alkyl cationic monomer.
Preferably, the polymerization reaction is carried out for 2-6 h at 70-90 ℃, and then sodium bisulfite solution is added.
Preferably, the mass of the sodium bisulfite is 1-3% of the total mass of the first component and the acrylamide alkyl cationic monomer.
Preferably, the pH is adjusted to 9.0-13.5 by sodium hydroxide.
It is to be noted that the invention selects acrylamide alkyl cationic monomer, and uses ammonium persulfate-sodium hypophosphite mixed initiation system to complete polymerization reaction under alkaline condition, which is obviously different from the traditional preparation method of amphoteric polymer using acrylamide alkyl quaternary ammonium salt cationic monomer (DMC, DAC, etc.) under acidic condition and using persulfate or redox system. This makes the amphoteric acrylic polymer retanning agent prepared by the invention completely clear at isoelectric point and no precipitate is generated.
Firstly, the amido bond in the cationic monomer used in the invention makes the nucleophilicity of the amphoteric acrylic polymer stronger than that of ester bonds in other cationic monomers, so that more positive charges can be obtained just after the pH value is reduced to be below the isoelectric point of the polymer, and stronger electrostatic repulsive force is generated, thereby promoting the polymer to have better solubility at the isoelectric point.
Secondly, the pH value of the polymerization reaction is controlled to be 9.0-13.5, which is obviously different from the prior art that the polymerization is carried out under the acidic condition. Applicants have found that under alkaline conditions, complete dissociation of the acrylic anionic monomer to a negative charge can generate sufficient electrostatic repulsive force to cause polymer molecules to have more extended chain segments and higher randomness during polymerization. Meanwhile, the cationic monomer is stable and not hydrolyzed under stronger alkaline conditions.
Finally, the invention adopts a mixed initiating system of ammonium persulfate-sodium hypophosphite, introduces specific phosphate groups into the molecular main chain/end group of the amphoteric acrylic polymer through the chain transfer effect of free radical polymerization, can better control the size of the polymer, and the phosphate groups can promote the polymer to be better dispersed in the solution, so that the finally prepared amphoteric polymer retanning agent achieves the effect of no precipitation at the isoelectric point.
The second technical scheme adopted by the invention is as follows: the amphoteric acrylic polymer retanning agent obtained by the first technical scheme is adopted.
Preferably, the isoelectric point of the amphoteric acrylic polymer retanning agent is 4.0-6.0.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, acrylamide alkyl cationic monomer with high polymerization activity and difficult hydrolysis is selected, and is subjected to polymerization reaction with amphoteric acrylic polymer under an alkaline condition by adopting an ammonium persulfate-sodium hypophosphite mixed initiation system, amide bond in the acrylamide alkyl cationic monomer in the reaction system can enable the amphoteric acrylic polymer to quickly obtain a large amount of positive charges just after the amphoteric acrylic polymer crosses an isoelectric point, so that stronger electrostatic repulsive force is generated to promote the polymer to have better solubility at the isoelectric point, the polymer chain of the obtained amphoteric acrylic polymer is more stretched and has higher random degree, the effect of no precipitation is achieved at the isoelectric point, the uniform distribution degree of the amphoteric acrylic polymer tanning agent in leather can be greatly improved, and the retanning application effect of the leather is obviously enhanced.
Drawings
FIG. 1 is a graph showing the distribution and particle size distribution of amphoteric acrylic polymer retanning agents in solution according to example 1 and comparative examples 1 to 6 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Preparation of amphoteric acrylic polymer retanning agent:
mixing and stirring 35 parts by weight of acrylic acid and 40 parts by weight of water, dropwise adding 85 parts by weight of methacryloyl propyl trimethyl ammonium chloride (MAPTAC) and NaOH solution, controlling the pH to be 9.0, dropwise adding 4 parts by weight of ammonium persulfate and 6 parts by weight of sodium hypophosphite which are dissolved by water at 90 ℃, carrying out polymerization reaction for 4 hours, adding 3 parts by weight of sodium bisulfite, and finally cooling to room temperature to obtain the amphoteric acrylic polymer retanning agent with the isoelectric point of 5.7.
Comparative example 1
Compared with example 1, except that methacrylylpropyltrimethylammonium chloride (MAPTAC) was replaced with an equal amount of methacryloyloxyethyltrimethylammonium chloride (DMC), the remaining parameters and methods were the same as in example 1, to obtain an amphoteric acrylic polymer retanning agent having an isoelectric point of 5.5.
Comparative example 2
Except that the pH of the solution was controlled to 6.0 and the remaining parameters and method were the same as in example 1, an amphoteric acrylic polymer retanning agent having an isoelectric point of 5.7 was obtained, as compared with example 1.
Comparative example 3
Except that the pH was controlled to 2.0 using HCl solution and the remaining parameters and method were the same as in example 1, an amphoteric acrylic polymer retanning agent having an isoelectric point of 5.7 was obtained, compared to example 1.
Comparative example 4
Compared to example 1, except that the initiator was replaced with 10 parts of ammonium persulfate and the remaining parameters and method were the same as in example 1, an amphoteric acrylic polymer retanning agent having an isoelectric point of 5.7 was obtained.
Comparative example 5
Compared with the example 1, the difference is only that the sodium hypophosphite in the initiator is replaced by the same amount of sodium sulfite, a redox system initiator is formed by the sodium hypophosphite and ammonium persulfate, and the rest parameters and the method are the same as the example 1, so that the amphoteric acrylic polymer retanning agent is obtained, and the isoelectric point of the amphoteric acrylic polymer retanning agent is 5.7.
Comparative example 6
Compared with the example 1, the difference is only that the initiator is replaced by 7 parts of redox system initiator consisting of 30% hydrogen peroxide, 0.5 part of ferrous sulfate and 2.5 parts of mercaptoethanol, and the rest parameters and methods are the same as the example 1, so that the amphoteric acrylic polymer retanning agent is obtained, and the isoelectric point of the amphoteric acrylic polymer retanning agent is 5.6.
Examples of the experiments
The aggregation state of the amphoteric acrylic polymer retanning agents prepared in example 1 and comparative examples 1-6 is observed, and the particle size and distribution of the amphoteric acrylic polymer retanning agents in the solution are tested by using a Dynamic Light Scattering (DLS) technology.
The test method is as follows: an amphoteric acrylic polymer solution with a concentration of 5 mg/mL is prepared, the pH of the solution is adjusted to the isoelectric point respectively, and the solution is measured by a multi-angle particle size and high-sensitivity Zeta potential analyzer (NanoBrook Omni, Brookhaven), the test angle is 90 degrees, the test time is 3 min, and the temperature is 25 ℃.
The test results are shown in table 1.
TABLE 1
Through the experiment, whether a mixed initiator system is replaced by a single initiator or a redox system initiator commonly used in the prior art, a cationic monomer in an embodiment is replaced by a cationic monomer with an ester group in the prior art, or the pH environment is replaced by acidity, and finally the obtained polymer generates precipitation at the isoelectric point.
Example 2
Preparation of amphoteric acrylic polymer retanning agent:
mixing and stirring 40 parts of acrylic acid and 50 parts of water according to parts by weight, dropwise adding 60 parts of dimethylaminopropyl methacrylamide (DMAPMA) and NaOH solution, controlling the pH to be 10.0, dropwise adding 1 part of ammonium persulfate and 0.1 part of sodium hypophosphite which are dissolved by water at 85 ℃, carrying out polymerization reaction for 6 hours, adding 1 part of sodium bisulfite, and finally cooling to room temperature to obtain the amphoteric acrylic polymer retanning agent, wherein the isoelectric point of the amphoteric acrylic polymer retanning agent is 4.8, the amphoteric acrylic polymer retanning agent is clear and transparent, has no sediment completely, and has the average particle size of 28 nm.
Example 3
Preparation of amphoteric acrylic polymer retanning agent:
mixing and stirring 38 parts by weight of acrylic acid and 45 parts by weight of water, dropwise adding 72 parts by weight of (3-acrylamidopropyl) trimethyl ammonium chloride and NaOH solution, controlling the pH to be 13.5, dropwise adding 5.5 parts by weight of ammonium persulfate and 2.5 parts by weight of sodium hypophosphite which are dissolved by water at 70 ℃, adding 3.3 parts by weight of sodium bisulfite after the total polymerization reaction time is 3.5 hours, and finally cooling to the room temperature to obtain the amphoteric acrylic polymer retanning agent, wherein the isoelectric point of the amphoteric acrylic polymer retanning agent is 4.6, the amphoteric acrylic polymer retanning agent is clear and transparent, has no precipitate at all, and has the average particle size of 20 nm.
Example 4
Preparation of amphoteric acrylic polymer retanning agent:
mixing and stirring 35 parts of methacrylic acid and 40 parts of water according to parts by weight, dropwise adding 25 parts of dimethylaminopropyl acrylamide (DMAPAA) and NaOH solution, controlling the pH to be 12.0, dropwise adding 3 parts of ammonium persulfate and 4.2 parts of sodium hypophosphite which are dissolved by water at 90 ℃, carrying out polymerization reaction for 2 hours, adding 1.8 parts of sodium bisulfite, and finally cooling to room temperature to obtain the amphoteric acrylic polymer retanning agent, wherein the isoelectric point of the amphoteric acrylic polymer retanning agent is 4.0, the amphoteric acrylic polymer retanning agent is clear and transparent, has no precipitate at all, and has the average particle size of 26 nm.
Example 5
Preparation of amphoteric acrylic polymer retanning agent:
mixing and stirring 45 parts of methacrylic acid and 50 parts of water according to parts by weight, dropwise adding 140 parts of methacryl propyl trimethyl ammonium chloride (MAPTAC) and NaOH solution, controlling the pH to be 11.0, dropwise adding 2 parts of ammonium persulfate and 3.7 parts of sodium hypophosphite which are dissolved by water at 80 ℃, carrying out polymerization reaction for 5 hours, adding 2 parts of sodium bisulfite, and finally cooling to room temperature to obtain the amphoteric acrylic polymer retanning agent, wherein the isoelectric point of the amphoteric acrylic polymer retanning agent is 6.0, the amphoteric acrylic polymer retanning agent is clear and transparent, has no sediment completely, and the average particle size is 15 nm.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. The preparation method of the amphoteric acrylic polymer retanning agent is characterized by comprising the following steps: mixing the first component with an acrylamide alkyl cationic monomer, controlling the pH to be 9.0-13.5, carrying out polymerization reaction under the action of an initiator, and cooling;
wherein the first component is acrylic acid or methacrylic acid;
the initiator is a mixed system of ammonium persulfate and sodium hypophosphite.
2. The method for preparing amphoteric acrylic polymer retanning agent according to claim 1, wherein the acrylamide alkyl cationic monomer comprises any one of dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, methacrylpropyltrimethylammonium chloride, and (3-acrylamidopropyl) trimethylammonium chloride.
3. The method for preparing amphoteric acrylic polymer retanning agent according to claim 1, wherein the first component is 35 to 45 parts by weight and the acrylamide alkyl cationic monomer is 25 to 140 parts by weight.
4. The method for preparing the amphoteric acrylic polymer retanning agent according to claim 1, wherein the mass of the ammonium persulfate is 1-5% of the total mass of the first component and the acrylamide alkyl cationic monomer, and the mass of the sodium hypophosphite is 0.1-7% of the total mass of the first component and the acrylamide alkyl cationic monomer.
5. The method for preparing the amphoteric acrylic polymer retanning agent according to claim 1, wherein the polymerization reaction is carried out at 70-90 ℃ for 2-6 h, and then sodium bisulfite solution is added.
6. The method for preparing the amphoteric acrylic polymer retanning agent according to claim 5, wherein the mass of the sodium bisulfite is 1 to 3% of the total mass of the first component and the acrylamide alkyl cationic monomer.
7. The method for preparing amphoteric acrylic polymer retanning agent according to claim 1, wherein the pH is adjusted to 9.0-13.5 with sodium hydroxide.
8. An amphoteric acrylic polymer retanning agent obtained by the production method according to any one of claims 1 to 7.
9. The amphoteric acrylic polymer retanning agent according to claim 8, wherein the isoelectric point of the amphoteric acrylic polymer retanning agent is 4.0 to 6.0.
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|---|---|---|---|---|
| US4961750A (en) * | 1987-07-27 | 1990-10-09 | Rohm Gmbh | Acrylate tanning agent |
| CN103276118A (en) * | 2013-05-08 | 2013-09-04 | 陕西科技大学 | Amphiprotic acrylic resin leather tanning agent |
| CN103570868A (en) * | 2013-10-25 | 2014-02-12 | 安徽循环经济技术工程院 | Aqueous solution polymerization preparation method for (meth)acrylamido propyl trimethyl ammonium chloride and acrylamide copolymer |
| CN111205408A (en) * | 2020-01-13 | 2020-05-29 | 兴业皮革科技股份有限公司 | Negative oxygen ion vinyl copolymer retanning agent, preparation method thereof and application of negative oxygen ion vinyl copolymer retanning agent in low-formaldehyde antibacterial leather |
| CN111961768A (en) * | 2020-07-24 | 2020-11-20 | 汤普勒新材料嘉兴有限公司 | Preparation method of amphoteric polyacrylic acid retanning agent |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4961750A (en) * | 1987-07-27 | 1990-10-09 | Rohm Gmbh | Acrylate tanning agent |
| CN103276118A (en) * | 2013-05-08 | 2013-09-04 | 陕西科技大学 | Amphiprotic acrylic resin leather tanning agent |
| CN103570868A (en) * | 2013-10-25 | 2014-02-12 | 安徽循环经济技术工程院 | Aqueous solution polymerization preparation method for (meth)acrylamido propyl trimethyl ammonium chloride and acrylamide copolymer |
| CN111205408A (en) * | 2020-01-13 | 2020-05-29 | 兴业皮革科技股份有限公司 | Negative oxygen ion vinyl copolymer retanning agent, preparation method thereof and application of negative oxygen ion vinyl copolymer retanning agent in low-formaldehyde antibacterial leather |
| CN111961768A (en) * | 2020-07-24 | 2020-11-20 | 汤普勒新材料嘉兴有限公司 | Preparation method of amphoteric polyacrylic acid retanning agent |
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